Regulating surface electron structure of PtNi nanoalloy via boron doping for high-current-density Li-O₂ batteries with low overpotential and long-life cyclability

Abstract

The realization of high-efficiency, reversible, stable, and safe Li-O₂ batteries is severely hindered by the large overpotential and side reactions, especially at high rate conditions. Therefore, rational design of cathode catalysts with high activity and stability is crucial to overcome the terrible issues at high current density. Herein, we report a surface engineering strategy to adjust the surface electron structure of boron (B)-doped PtNi nanoalloy on carbon nanotubes (PtNiB@CNTs) as an efficient bifunctional cathodic catalyst for high-rate and long-life Li-O₂ batteries. Notably, the Li-O₂ batteries assembled with as-prepared PtNiB@CNT catalyst exhibit ultrahigh discharge capacity of 20510 mA·h/g and extremely low overpotential of 0.48 V at a high current density of 1000 mA/g, both of which outperform the most reported Pt-based catalysts recently. Meanwhile, our Li-O₂ batteries offer excellent rate capability and ultra-long cycling life of up to 210 cycles at 1000 mA/g under a fixed capacity of 1000 mA·h/g, which is two times longer than those of Pt@CNTs and PtNi@CNTs. Furthermore, it is revealed that surface engineering of PtNi nanoalloy via B doping can efficiently tailor the electron structure of nanoalloy and optimize the adsorption of oxygen species, consequently delivering excellent Li-O₂ battery performance. Therefore, this strategy of regulating the nanoalloy by doping nonmetallic elements will pave an avenue for the design of high-performance catalysts for metal-oxygen batteries.

Keywords

B doping / bifunctional catalyst / Li-O₂ battery / low charge overpotential / PtNi nanoalloy

References

[1] Goodenough JB, Park K-S. The Li-ion rechargeable battery: a perspective. J Am Chem Soc. 2013;135:1167-1176.

[2] Etacheri V, Marom R, Elazari R, Salitra G, Aurbach D. Challenges in the development of advanced Li-ion batteries: a review. Energy Environ Sci. 2011;4:3243-3262.

[3] Li M, Lu J, Chen ZW, Amine K. 30 years of lithium-ion batteries. Adv Mater. 2018;30:1800561.

[4] Li T, Peng X, Cui P, et al. Recent progress and future perspectives of flexible metal-air batteries. SmartMat. 2021;2:519-553.

[5] Liu B, Zhang JG, Xu W. Advancing lithium metal batteries. Joule. 2018;2:833-845.

[6] Wu M, Li Y, Liu X, Yang S, Ma J, Dou S. Perspective on solid-electrolyte interphase regulation for lithium metal batteries. SmartMat. 2021;2:5-11.

[7] Kwak W-J, Rosy , Sharon D, et al. Lithium-oxygen batteries and related systems: potential, status, and future. Chem Rev. 2020;120:6626-6683.

[8] Liu T, Vivek JP, Zhao EW, Lei J, Garcia-Araez N, Grey CP. Current challenges and routes forward for nonaqueous lithium-air batteries. Chem Rev. 2020;120:6558-6625.

[9] Girishkumar G, McCloskey B, Luntz AC, Swanson S, Wilcke W. Lithium-air battery: promise and challenges. J Phys Chem Lett. 2010;1:2193-2203.

[10] Lu Y-C, Gallant BM, Kwabi DG, et al. Lithium-oxygen batteries: bridging mechanistic understanding and battery performance. Energy Environ Sci. 2013;6:750-768.

[11] Capsoni D, Bini M, Ferrari S, Quartarone E, Mustarelli P. Recent advances in the development of Li-air batteries. J Power Sources. 2012;220:253-263.

[12] Thotiyl MMO, Freunberger SA, Peng Z, Chen Y, Liu Z, Bruce PG. A stable cathode for the aprotic Li-O₂ battery. Nat Mater. 2013;12:1049-1055.

[13] Ma Z, Yuan X, Li L, et al. A review of cathode materials and structures for rechargeable lithium-air batteries. Energy Environ Sci. 2015;8:2144-2198.

[14] Guo X, Sun B, Su D, et al. Recent developments of aprotic lithium-oxygen batteries: functional materials determine the electrochemical performance. Sci Bull. 2017;62:442-452.

[15] Xu J-J, Zhang X-B. Li-air batteries: decouple to stabilize. Nat Energy. 2017;2:17133.

[16] Oh SH, Black R, Pomerantseva E, Lee J-H, Nazar LF. Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium-O₂ batteries. Nat Chem. 2012;4:1004-1010.

[17] Lim H-D, Lee B, Zheng Y, et al. Rational design of redox mediators for advanced Li-O₂ batteries. Nat Energy. 2016;1:16066.

[18] Zhou Y, Yan D, Gu Q, et al. Implanting cation vacancies in Ni-Fe LDHs for efficient oxygen evolution reactions of lithium-oxygen batteries. Appl Catal B. 2021;285:119792.

[19] Liao K, Wang X, Sun Y, et al. An oxygen cathode with stable full discharge-charge capability based on 2D conducting oxide. Energy Environ Sci. 2015;8:1992-1997.

[20] Wang Y, Wang D, Li Y. A fundamental comprehension and recent progress in advanced Pt-based ORR nanocatalysts. SmartMat. 2021;2:56-75.

[21] Luo M, Zhao Z, Zhang Y, et al. PdMo bimetallene for oxygen reduction catalysis. Nature. 2019;574:81-85.

[22] Peng Z, Freunberger SA, Chen Y, Bruce PG. A reversible and higher-rate Li-O₂ battery. Science. 2012;337:563-566.

[23] Wu F, Xing Y, Zeng X, et al. Platinum-coated hollow graphene nanocages as cathode used in lithium-oxygen batteries. Adv Funct Mater. 2016;26:7626-7633.

[24] Lei Y, Lu J, Luo X, et al. Synthesis of porous carbon supported palladium nanoparticle catalysts by atomic layer deposition: application for rechargeable lithium-O₂ battery. Nano Lett. 2013;13:4182-4189.

[25] Zhao C, Yu C, Banis MN, et al. Decoupling atomic-layer-deposition ultrafine RuO₂ for high-efficiency and ultralong-life Li-O₂ batteries. Nano Energy. 2017;34:399-407.

[26] Hong J, Hyun S, Tsipoaka M, Samdani JS, Shanmugam S. RuFe alloy nanoparticle-supported mesoporous carbon: efficient bifunctional catalyst for Li-O₂ and Zn-air batteries. ACS Catal. 2022;12:1718-1731.

[27] Li T, Dong Q, Huang Z, et al. Interface engineering between multi-elemental alloy nanoparticles and a carbon support toward stable catalysts. Adv Mater. 2022;34:2106436.

[28] Ma L, Luo X, Kropf AJ, et al. Insight into the catalytic mechanism of bimetallic platinum–copper core-shell nanostructures for nonaqueous oxygen evolution reactions. Nano Lett. 2016;16:781-785.

[29] Luo X, Ge L, Ma L, et al. Effect of componential proportion in bimetallic electrocatalysts on the aprotic lithium-oxygen battery performance. Adv Energy Mater. 2018;8:1703230.

[30] Tan G, Chong L, Zhan C, et al. Insights into structural evolution of lithium peroxides with reduced charge overpotential in Li-O₂ system. Adv Energy Mater. 2019;9:1900662.

[31] Dong H, Tang P, Wang X, et al. Pt/NiO microsphere composite as efficient multifunctional catalysts for nonaqueous lithium-oxygen batteries and alkaline fuel cells: the synergistic effect of Pt and Ni. ACS Appl Mater Interfaces. 2019;11:39789-39797.

[32] Wang N, Xu A, Ou P, et al. Boride-derived oxygen-evolution catalysts. Nat Commun. 2021;12:6089.

[33] Gupta S, Patel MK, Miotello A, Patel N. Metal boride-based catalysts for electrochemical water-splitting: a review. Adv Funct Mater. 2020;30:1906481.

[34] Li Q, Liu C, Qiu S, et al. Exploration of iron borides as electrochemical catalysts for the nitrogen reduction reaction. J Mater Chem A. 2019;7:21507-21513.

[35] Skrabalak SE, Suslick KS. On the possibility of metal borides for hydrodesulfurization. Chem Mater. 2006;18:3103-3107.

[36] Wang L, Li J, Zhao X, et al. Surface-activated amorphous iron borides (Fe_xB) as efficient electrocatalysts for oxygen evolution reaction. Adv Mater Interfaces. 2019;6:1801690.

[37] Masa J, Andronescu C, Antoni H, et al. Role of boron and phosphorus in enhanced electrocatalytic oxygen evolution by nickel borides and nickel phosphides. ChemElectroChem. 2019;6:235-240.

[38] Gupta S, Jadhav H, Sinha S, et al. Cobalt-boride nanostructured thin films with high performance and stability for alkaline water oxidation. ACS Sustainable Chem Eng. 2019;7:16651-16658.

[39] Zhou Y, Gao Y, Zhong X, et al. Electrocatalytic upgrading of lignin-derived bio-oil based on surface-engineered PtNiB nanostructure. Adv Funct Mater. 2019;29:1807651.

[40] Masa J, Sinev I, Mistry H, et al. Ultrathin high surface area nickel boride (Ni_xB) nanosheets as highly efficient electrocatalyst for oxygen evolution. Adv Energy Mater. 2017;7:1700381.

[41] Ding Y, Sun W, Yang W, Li Q. Formic acid as the in-situ hydrogen source for catalytic reduction of nitrate in water by PdAg alloy nanoparticles supported on amine-functionalized SiO₂. Appl Catal B. 2017;203:372-380.

[42] Lu J, Lee YJ, Luo X, et al. A lithium-oxygen battery based on lithium superoxide. Nature. 2016;529:377-382.

[43] Lim H-D, Song H, Gwon H, et al. A new catalyst-embedded hierarchical air electrode for high-performance Li-O₂ batteries. Energy Environ Sci. 2013;6:3570-3575.

[44] Xia H, Xie Q, Tian Y, et al. High-efficient CoPt/activated functional carbon catalyst for Li-O₂ batteries. Nano Energy. 2021;84:105877.

[45] Kumar S, Munichandraiah N. Nanoparticles of a Pt₃Ni alloy on reduced graphene oxide (RGO) as an oxygen electrode catalyst in a rechargeable Li-O₂ battery. Mater Chem Front. 2017;1:873-878.

[46] Jung WB, Park H, Jang JS, et al. Polyelemental nanoparticles as catalysts for a Li-O₂ battery. ACS Nano. 2021;15:4235-4244.

[47] Li X, Zhao Y, Zhang J, et al. Iridic oxide nanoparticles grown in situ on BCN nanotubes as highly efficient dual electrocatalyst for rechargeable lithium-O₂ batteries. J Energy Chem. 2020;49:291-298.

[48] Li X, Wen C, Li H, Sun G. In situ decoration of nanosized metal oxide on highly conductive MXene nanosheets as efficient catalyst for Li-O₂ battery. J Energy Chem. 2020;47:272-280.

[49] Hu X, Luo G, Zhao Q, et al. Ru single atoms on N-doped carbon by spatial confinement and ionic substitution strategies for high-performance Li-O₂ batteries. J Am Chem Soc. 2020;142:16776-16786.

[50] Yao W, Yuan Y, Tan G, et al. Tuning Li₂O₂ formation routes by facet engineering of MnO₂ cathode catalysts. J Am Chem Soc. 2019;141:12832-12838.

[51] Wang M, Liu S, Qian T, et al. Over 56.55% Faradaic efficiency of ambient ammonia synthesis enabled by positively shifting the reaction potential. Nat Commun. 2019;10:341.

[52] Jiang C, Zhang Y, Shen H, Liu C. Target-regulated Ce³⁺/Ce⁴⁺ redox switch for fluorescence turn-on detection of H₂O₂ and glucose. ChemistrySelect. 2017;2:9181-9185.

[53] Wang JS, Guo CR, Cheng YX. Mechanism of cerium ions scavenging superoxide radical. J Rare Earths. 1998;16:46-50.

[54] Zhao D, Wang P, Di H, Zhang P, Hui X, Yin L. Single semi-metallic selenium atoms on Ti₃C₂ MXene nanosheets as excellent cathode for lithium-oxygen batteries. Adv Funct Mater. 2021;31:2010544.

RIGHTS & PERMISSIONS

2022 2022 The Authors. SmartMat published by Tianjin University and John Wiley & Sons Australia, Ltd.